Financial support for this work is acknowledged (grant nos. CTQ2007-61048 and IB08-088). S.S.-P. and D.P. thank the MICINN for predoctoral FPU fellowships. We also thank Dr. Ángel L. Suárez-Sobrino for his helpful assistance with the X-ray analysis. We are grateful to the referees for their kind and helpful suggestions to improve the manuscript, particularly for the labeling experiments.

Keywords:

carbocycles;

heterocycles;

hydroarylation;

Lewis acids;

propargylic esters

Doubling the bet: Two CH bonds become functionalized upon exposure of ω-aryl propargylic tosylates to Sc(OTf)3 (see scheme). The reaction involves a new domino process that can tolerate both electron-withdrawing and -donating substituents on the arene unit. Different carbo- and heterocyclic frameworks can be assembled by using this approach to formally conquer the hydroarylation process.